3,4,5-Trihy­droxy­benzohydrazide

Ashiq, U.; Ara Jamal, R.; Yousuf, S.

doi:10.1107/S1600536811034374

organic compounds

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Volume 67| Part 9| September 2011| Page o2462

doi:10.1107/S1600536811034374

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3,4,5-Trihydroxybenzohydrazide

Uzma Ashiq,^a ^* Rifat Ara Jamal ^a and Sammer Yousuf ^b

^aDepartment of Chemistry, University of Karachi, Karachi-75270, Pakistan, and ^bHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi-75270, Pakistan
^*Correspondence e-mail: uzzmma@yahoo.com

(Received 12 August 2011; accepted 21 August 2011; online 27 August 2011)

In the title compound, C₇H₈N₂O₄, the dihedral angle between the aromatic ring and the hydrazide grouping is 21.34 (7)°. In the crystal, the molecules are linked into a three-dimensional network by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds.

Related literature

For the biological activity of hydrazides, see: Maqsood et al. (2006 ). For related structures, see: Jamal et al. (2009 ); Saeed et al. (2008 ); Zareef et al. (2006 ).

Experimental

Crystal data

C₇H₈N₂O₄
M_r = 184.15
Monoclinic, P 2₁ /c
a = 3.7307 (3) Å
b = 22.8402 (18) Å
c = 8.7064 (7) Å
β = 93.290 (2)°
V = 740.65 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 273 K
0.28 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.963, T_max = 0.973
4345 measured reflections
1352 independent reflections
1234 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.092
S = 1.09
1352 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2ⁱ	0.85 (3)	2.09 (2)	2.8254 (14)	145.0 (19)
N1—H1B⋯O1ⁱⁱ	0.86 (2)	2.24 (2)	2.9960 (15)	146.2 (16)
O2—H2A⋯N2ⁱⁱⁱ	0.91 (3)	1.80 (2)	2.6877 (17)	165 (2)
N2—H2B⋯O3^iv	0.88 (2)	2.25 (2)	3.1158 (17)	167.0 (18)
N2—H2C⋯O4^v	0.92 (2)	2.454 (18)	3.2255 (18)	141.8 (15)
O3—H3A⋯O4^vi	0.89 (2)	1.77 (2)	2.6522 (15)	171 (2)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+2, -y+1, -z+1; (iii) x-1, y, z+1; (iv) x, y, z-1; (v) x+1, y, z; (vi) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034374/hb6363sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034374/hb6363Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034374/hb6363Isup3.cml

checkCIF report

Comment top

In order to further explore the biological significance of hydrazides, we have prepared the title compound (I). It was found to be active against DPPH radical scavenging activity and inactive against all fungal strains (Maqsood et al. 2006). The crystal structures of trimethoxybenzohydrazide (Saeed et al. 2008, Zareef et al. 2006) and para hydroxybenzohydrazide (Jamal et al. 2009) analogues of (I) have already been reported.

The molecular structure of (I) is composed of a hydrazide moiety attached to the phenyl ring (Fig. 1). The phenyl ring is almost planar with a maximum deviation of 0.009 (1) Å from the least-squares plane. The bond lengths and angles all are in normal range as in other structurally related compounds (Saeed et al. 2008; Zareef et al., 2006). In the crystal, the molecules are linked to form three-dimensional molecular network via O1—H1A···O2, N1—H1B···O1, O2—H2A···N2, N2—H2B···O3, N2—H2C···O4 and O3—H3A···O4 intermolecular hydrogen bonds (Tab. 1 & Fig. 2).

Related literature top

For biological background, see: Maqsood et al. (2006). For related structures, see: Jamal et al. (2009); Saeed et al. (2008); Zareef et al., (2006).

Experimental top

To a solution of methyl-3,4,5-trihydroxybenzoate (3.68 g, 20 mmol) in 75 ml ethanol, hydrazine hydrate (5.0 ml, 100 mmol) was added. The mixture was refluxed for 5 h and a solid was obtained upon removal of the solvent by rotary evaporation. The resulting solid was washed with hexane to afford 3,4,5-trihydroxybenzohydrazide (yield 87%) (Maqsood et al., 2006). Colourless blocks of (I) were grown from a solution of methanol by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 50% probability level.
	Fig. 2. The crystal packing of the title compound I. Only hydrogen atoms involved in hydrogen bonding are shown.

3,4,5-Trihydroxybenzohydrazide top

Crystal data top

C₇H₈N₂O₄	F(000) = 384
M_r = 184.15	D_x = 1.651 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2464 reflections
a = 3.7307 (3) Å	θ = 3.0–28.3°
b = 22.8402 (18) Å	µ = 0.14 mm⁻¹
c = 8.7064 (7) Å	T = 273 K
β = 93.290 (2)°	Block, colorles
V = 740.65 (10) Å³	0.28 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1352 independent reflections
Radiation source: fine-focus sealed tube	1234 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scan	θ_max = 25.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −4→4
T_min = 0.963, T_max = 0.973	k = −27→26
4345 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0509P)² + 0.2069P] where P = (F_o² + 2F_c²)/3
1352 reflections	(Δ/σ)_max = 0.001
150 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₇H₈N₂O₄	V = 740.65 (10) Å³
M_r = 184.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.7307 (3) Å	µ = 0.14 mm⁻¹
b = 22.8402 (18) Å	T = 273 K
c = 8.7064 (7) Å	0.28 × 0.21 × 0.20 mm
β = 93.290 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1352 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1234 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.973	R_int = 0.016
4345 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.18 e Å⁻³
1352 reflections	Δρ_min = −0.24 e Å⁻³
150 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.6088 (3)	0.49395 (4)	0.75022 (12)	0.0388 (3)
O2	0.4790 (3)	0.57014 (4)	0.97692 (11)	0.0328 (3)
H2A	0.375 (6)	0.5994 (11)	1.029 (3)	0.069 (7)*
O3	0.5451 (3)	0.68880 (5)	0.93130 (11)	0.0334 (3)
H3A	0.602 (6)	0.7255 (10)	0.907 (2)	0.061 (6)*
O4	0.7876 (3)	0.70585 (5)	0.36218 (12)	0.0402 (3)
N1	1.0268 (3)	0.62028 (5)	0.30646 (13)	0.0270 (3)
H1B	1.100 (5)	0.5854 (9)	0.329 (2)	0.037 (5)*
N2	1.1408 (4)	0.64212 (6)	0.16535 (13)	0.0283 (3)
H2C	1.285 (5)	0.6739 (9)	0.188 (2)	0.041 (5)*
H2B	0.950 (6)	0.6553 (8)	0.112 (2)	0.044 (5)*
C1	0.7698 (4)	0.63145 (6)	0.55422 (14)	0.0224 (3)
C2	0.7029 (4)	0.67156 (6)	0.66914 (15)	0.0250 (3)
H2	0.718 (4)	0.7128 (8)	0.6488 (18)	0.031 (4)*
C3	0.6093 (4)	0.65203 (6)	0.81195 (14)	0.0235 (3)
C4	0.5743 (4)	0.59242 (6)	0.84021 (14)	0.0231 (3)
C5	0.6437 (4)	0.55257 (6)	0.72421 (15)	0.0244 (3)
C6	0.7421 (4)	0.57157 (6)	0.58183 (15)	0.0246 (3)
H6	0.780 (4)	0.5428 (7)	0.5049 (19)	0.030 (4)*
C7	0.8618 (4)	0.65546 (6)	0.40269 (14)	0.0239 (3)
H1A	0.548 (6)	0.4893 (9)	0.842 (3)	0.057 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0733 (9)	0.0179 (5)	0.0271 (6)	0.0005 (5)	0.0199 (5)	0.0016 (4)
O2	0.0557 (7)	0.0214 (5)	0.0230 (5)	0.0030 (5)	0.0173 (5)	0.0034 (4)
O3	0.0602 (8)	0.0190 (5)	0.0227 (5)	−0.0028 (5)	0.0169 (5)	−0.0024 (4)
O4	0.0707 (9)	0.0224 (5)	0.0295 (6)	0.0123 (5)	0.0199 (5)	0.0066 (4)
N1	0.0409 (8)	0.0210 (6)	0.0202 (6)	0.0058 (5)	0.0118 (5)	0.0038 (4)
N2	0.0388 (8)	0.0276 (7)	0.0194 (6)	0.0021 (6)	0.0105 (5)	0.0028 (5)
C1	0.0257 (7)	0.0229 (7)	0.0190 (6)	0.0014 (5)	0.0045 (5)	0.0011 (5)
C2	0.0332 (8)	0.0188 (7)	0.0235 (7)	−0.0002 (6)	0.0063 (5)	0.0012 (5)
C3	0.0291 (8)	0.0211 (7)	0.0209 (6)	0.0002 (5)	0.0061 (5)	−0.0016 (5)
C4	0.0280 (8)	0.0225 (7)	0.0194 (6)	0.0006 (5)	0.0062 (5)	0.0023 (5)
C5	0.0317 (8)	0.0177 (7)	0.0241 (7)	0.0009 (5)	0.0055 (5)	0.0014 (5)
C6	0.0322 (8)	0.0218 (7)	0.0205 (7)	0.0027 (6)	0.0064 (5)	−0.0023 (5)
C7	0.0302 (8)	0.0211 (7)	0.0207 (6)	0.0001 (5)	0.0047 (5)	0.0000 (5)

Geometric parameters (Å, º) top

O1—C5	1.3654 (16)	N2—H2B	0.88 (2)
O1—H1A	0.85 (2)	C1—C2	1.3897 (18)
O2—C4	1.3603 (16)	C1—C6	1.3934 (19)
O2—H2A	0.91 (3)	C1—C7	1.4869 (17)
O3—C3	1.3678 (16)	C2—C3	1.3844 (18)
O3—H3A	0.89 (2)	C2—H2	0.961 (18)
O4—C7	1.2306 (17)	C3—C4	1.3912 (19)
N1—C7	1.3363 (18)	C4—C5	1.3946 (19)
N1—N2	1.4139 (15)	C5—C6	1.3828 (19)
N1—H1B	0.860 (19)	C6—H6	0.955 (17)
N2—H2C	0.92 (2)

C5—O1—H1A	108.1 (14)	O3—C3—C2	123.28 (12)
C4—O2—H2A	107.7 (15)	O3—C3—C4	116.38 (11)
C3—O3—H3A	110.1 (14)	C2—C3—C4	120.35 (12)
C7—N1—N2	120.34 (12)	O2—C4—C3	123.55 (12)
C7—N1—H1B	124.6 (12)	O2—C4—C5	117.28 (12)
N2—N1—H1B	114.4 (12)	C3—C4—C5	119.17 (12)
N1—N2—H2C	107.3 (11)	O1—C5—C6	119.29 (12)
N1—N2—H2B	107.8 (12)	O1—C5—C4	119.76 (12)
H2C—N2—H2B	106.7 (17)	C6—C5—C4	120.95 (12)
C2—C1—C6	120.31 (12)	C5—C6—C1	119.26 (12)
C2—C1—C7	117.11 (12)	C5—C6—H6	118.0 (10)
C6—C1—C7	122.56 (12)	C1—C6—H6	122.7 (10)
C3—C2—C1	119.94 (13)	O4—C7—N1	119.12 (12)
C3—C2—H2	120.1 (9)	O4—C7—C1	122.66 (12)
C1—C2—H2	119.9 (9)	N1—C7—C1	118.21 (12)

C6—C1—C2—C3	0.2 (2)	C3—C4—C5—C6	−0.8 (2)
C7—C1—C2—C3	178.80 (13)	O1—C5—C6—C1	178.56 (13)
C1—C2—C3—O3	178.95 (13)	C4—C5—C6—C1	−0.4 (2)
C1—C2—C3—C4	−1.4 (2)	C2—C1—C6—C5	0.7 (2)
O3—C3—C4—O2	0.5 (2)	C7—C1—C6—C5	−177.85 (13)
C2—C3—C4—O2	−179.16 (13)	N2—N1—C7—O4	5.1 (2)
O3—C3—C4—C5	−178.65 (13)	N2—N1—C7—C1	−175.85 (13)
C2—C3—C4—C5	1.7 (2)	C2—C1—C7—O4	−20.3 (2)
O2—C4—C5—O1	1.0 (2)	C6—C1—C7—O4	158.29 (15)
C3—C4—C5—O1	−179.71 (13)	C2—C1—C7—N1	160.76 (13)
O2—C4—C5—C6	179.99 (13)	C6—C1—C7—N1	−20.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.85 (3)	2.09 (2)	2.8254 (14)	145.0 (19)
N1—H1B···O1ⁱⁱ	0.86 (2)	2.24 (2)	2.9960 (15)	146.2 (16)
O2—H2A···N2ⁱⁱⁱ	0.91 (3)	1.80 (2)	2.6877 (17)	165 (2)
N2—H2B···O3^iv	0.88 (2)	2.25 (2)	3.1158 (17)	167.0 (18)
N2—H2C···O4^v	0.92 (2)	2.454 (18)	3.2255 (18)	141.8 (15)
O3—H3A···O4^vi	0.89 (2)	1.77 (2)	2.6522 (15)	171 (2)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z+1; (iv) x, y, z−1; (v) x+1, y, z; (vi) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O₄
M_r	184.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	3.7307 (3), 22.8402 (18), 8.7064 (7)
β (°)	93.290 (2)
V (Å³)	740.65 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.28 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.963, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	4345, 1352, 1234
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.09
No. of reflections	1352
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.24

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.85 (3)	2.09 (2)	2.8254 (14)	145.0 (19)
N1—H1B···O1ⁱⁱ	0.86 (2)	2.24 (2)	2.9960 (15)	146.2 (16)
O2—H2A···N2ⁱⁱⁱ	0.91 (3)	1.80 (2)	2.6877 (17)	165 (2)
N2—H2B···O3^iv	0.88 (2)	2.25 (2)	3.1158 (17)	167.0 (18)
N2—H2C···O4^v	0.92 (2)	2.454 (18)	3.2255 (18)	141.8 (15)
O3—H3A···O4^vi	0.89 (2)	1.77 (2)	2.6522 (15)	171 (2)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z+1; (iv) x, y, z−1; (v) x+1, y, z; (vi) x, −y+3/2, z+1/2.

Acknowledgements

The authors are grateful to the Higher Education Commission (HEC) Pakistan for financial support under the National Research Grants Program for Universities (grant No. 1862/R&D/10).

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